National Environmental Research InstituteMinistry of the Environment . Denmark

Air QualityMonitoring ProgrammeAnnual Summary for 2002

NERI Technical Report No. 450

Kåre KempFinn Palmgren

National Environmental Research InstituteMinistry of the Environment . Denmark

Air QualityMonitoring ProgrammeAnnual Summary for 2002

NERI Technical Report No. 4502003

Kåre KempFinn Palmgren

2

Data sheet

Title: Air Quality Monitoring ProgrammeSubtitle: Annual Summary for 2002

Authors: Kåre Kemp, Finn PalmgrenDepartment: Department of Atmospheric Environment

Serial title and no.: NERI Technical Report No. 450

Publisher: National Environmental Research Institute Ministry of the Environment

URL: http://www.dmu.dk

Date of publication: August 2003

Referee: Peter Wåhlin

Technical assistance: Axel Egeløv, Lone Grundahl

Laboratorieassistance: Axel Egeløv, Lone Grundahl, Bjarne Jensen, Christina F. Emborg, Hanne Langberg,Jens Tscherning Møller, Birgit Thomsen, Jane Søfting, Lizzi Stausgaard

Financial support: Ministry of the Environment

Please cite as: Kemp, K. & Palmgren, F. 2003: The Danish Air Quality Monitoring Programme. An-nual Summary for 2002. National Environmental Research Institute, Roskilde Den-mark. 36 pp. -NERI Technical Report No .450. http:\\technical-reports.dmu.dk

Reproduction is permitted, provided the source is explicitly acknowledged.

Abstract: The air quality in Danish cities has been monitored continuously since 1982 withinthe Danish Air Quality (LMP) network. The aim has been to follow the concentrationlevels of toxic pollutants in the urban atmosphere and to provide the necessaryknowledge to assess the trends, to perform source apportionment, and to evaluatethe chemical reactions and the dispersion of the pollutants in the atmosphere. In 2002the air quality was measured in four Danish cities and at two background sites. NO2

and PM10 were at several stations found in concentrations above the new EU limitvalues, which the Member States have to comply with in 2005 and 2010. While theconcentrations for most other pollutants have been strongly decreasing since 1982,only a slight decrease has been observed for NO2.

Keywords: Atmospheric pollution, urban pollution, nitrogen compounds, ozone, sulphur com-pounds, heavy metals, volatile organic pollutants

Layout: Majbritt Pedersen-Ulrich

ISBN: 87-7772-746-0ISSN (electronic): 1600-0048

Number of pages: 36

Internet-version: The report is available only in electronic format from NERI’s homepagehttp://www.dmu.dk/1_viden/2_Publikationer/3_fagrapporter/rapporter/FR450.pdf

For sale at: MiljøbutikkenInformation and BooksStrandgade 29DK-1401Copenhagen KTel. +45 32 66 02 00Fax +45 33 92 76 90www.frontlinien.dk

3

Contents

Summary 5

1 Introduction 7

2 Measurements 9

3 Nitrogen oxides 113.1 Yearly Statistics 113.2 Episodes 133.3 Trends 14

4 Ozone 174.1 Annual statistics 174.2 Trends 18

5 Carbon monoxide 195.1 Annual statistics 195.2 Trends 20

6 Benzene and Toluene 216.1 Annual statistics 21

7 Particles (TSP, PM10) 237.1 Annual statistics 237.2 Trends 23

8 Heavy Metals 258.1 Annual statistics 258.2 Trends 26

9 Sulphur Compounds 279.1 Annual statistics 279.2 Trends 28

References 31

Danish summary - Dansk resumé 33

Appendix 35

4

5

Summary

The Danish Air Quality Monitoring Programme (LMP IV) has beenrevised in accordance with the Framework Directive and the firstthree daughter directives of SO2, NOx/NO2, PM10, lead, benzene, COand ozone. Only a PM10 monitor at an urban background location inOdense is missing. The data sets for year 2002 are almost complete forall stations. The monitoring programme consists of 10 stations plus 2extra stations under the Municipality of Copenhagen.

The limit value of the annual average of NO2 was in 2002 exceeded atthree street stations. At one station (Copenhagen/1103) the limitvalue + the margin of tolerance (58 µg/m3 in 2002) was exceeded. Thetrend seems to have been stabilised after several years of decrease.

The ozone level was in 2002 - more or less - the same at all rural andurban background stations and no clear trend is observed. The in-formation threshold on 180 µg/m3 was not exceeded. The target val-ues were not exceeded, but the long-term objectives of max 8 hourson 120 µg/m3 were exceeded at all urban background and rural sta-tions. The long term objective for AOT40 at 6000 µg/m3 *hours wereexceeded in a few cases.

The limit value of PM10 on 50 µg/m3, not to be exceeded more than 35times per year and to comply with in 2005, was in 2002 exceeded at 3out of 4 street stations. At all stations both limits values to be met in2010 (annual average value on 20 µg/m3 and 50 µg/m3 not to be ex-ceeded more than 7 times per year) were exceeded at all stations (in-cluding the rural station Keldsnor). PM10 is 60-70% of TSP. The trendof TSP has been clear decreasing the last 15 years.

The SO2 and lead levels are still decreasing and far below the limitvalues. The limit values for benzene and CO are not exceeded and thelevels are close to the levels in year 2001.

Actual data, quarterly reports, annual summaries and summariesover many year are available at the homepage of NERI on“luft.dmu.dk”.

6

7

1 Introduction

The fourth Danish Air Quality Monitoring Programme (LMP IV) wasstarted in 2000. The programme comprises an urban monitoring net-work with stations in four largest Danish cities, Figure 2-1. The resultsare used for assessment of the air pollution in urban areas. The pro-gramme is carried out in a co-operation between the National En-vironmental Research Institute (NERI), the Danish EnvironmentalProtection Agency, the Environmental Protection Agency of the Mu-nicipality in Copenhagen, the Municipality of Århus, the County ofFunen (for the city of Odense) and the Municipality of Aalborg. NERIis responsible for the practical programme. The results are currentlypublished in quarterly reports in Danish and they are summarised inannual reports in English and Danish. This report includes resultsfrom the LMP network and a local network in Greater Copenhagenorganised by the Environmental Protection Agency of the Municipal-ity in Copenhagen. Statistical parameters and actual data are accessi-ble at the Web address: luft.dmu.dk. Selected actual data are alsoavailable at tele-text, Danish National Television.

Two other air quality monitoring networks are in operation in Den-mark. The Environmental Protection Agency of the Municipality inCopenhagen is responsible for a network in the central part of Co-penhagen. A number of pollutants are measures at two sites. Themeasurements are comparable with the LMP measurements and thetwo programmes are under the same quality control/quality assur-ance and supplement each other in Copenhagen. A network in ruralareas (the Danish Background Monitoring Program) was establishedin 1978, Figure 2-1. NERI runs this programme. At present gas andaerosol measurements are performed at six stations, and various ionsare determined in precipitation collected at 12 sites. The aim is i.a. tostudy acidification and eutrofication of the forests, farmland, Danishsea and freshwater areas.

The present Danish limit values are identical with the limit valueslaid down in the EU directives. The new EU legislation consists of theframework directive (EC 1996), giving general rules for network de-sign and limit value strategies, and a number of daughter directivesgiving limit values, target values, alert thresholds, reference methodsand monitoring strategies for specific pollutants. The limit values areclose to the recommendations (WHO, 2000) based on the knownhealth effects of the pollutants. The limit values shall in most cases bereached in 2005 or 2010. Until then a so-called margin of tolerance areadded to the limit values. The margin of tolerance is gradually re-duced to zero at the date of compliance. Daughter Directives for NO2,SO2, particulate matter (PM10) and Pb (EC, 1999), CO and benzene(EC, 2000) and O3 (EC 2002) are presently adopted. A Directive for Cr,As, Cd and PAH is under preparation. In the following chapters themeasured results are compared to the limit values. Please refer to theDirectives for a detailed description of the exact definitions of thelimit values, margin of tolerance, target values and alert thresholds.

LMP IV

Other air quality networksin Denmark

New limit valuesimplemented by the EUCommission

8

9

2 Measurements

The measuring strategy is in short to place one or more pairs of sta-tions in each city. One of the stations is located close (at the sidewalk)to a street lane with a high traffic density. The other is located withina few hundred meters from the street station, and is representativefor the urban background pollution; it is not influenced by a single ora few streets or other nearby sources. In most cases the backgroundstations are placed on rooftops. Further two stations monitor thepollution outside the city areas. Further information about the pro-gram and results is found at the Web address: LUFT.DMU.DK.

N

Background Network

Urban Network (LMP)trafficurban backgroundrural

100 km

Aalborg

Århus

Lille ValbyKøben-havn

Odense

Keldsnor

Figure 2-1 Monitoring stations in the two nation-wide air quality networks.

Station locations

10

− NO, NOx, PM10 and elements (heavy metals) in PM10 were meas-ured at all stations (the PM10 not started yet at Odense/9159, TSPmeasured in stead of PM10 at Copenhagen/1103)

− O3 was measured at all urban background stations, Copenha-gen/1257 and Copenhagen/1103

− CO was measured at all street stations and Copenhagen/1259

− Benzene and Toluene were measured at Copenhagen/1257

− SO2 was measured at Aalborg/8151 and at Copenhagen/1103. Themain purpose is to monitor episodic high concentration.

− The meteorological parameters - temperature, wind speed and di-rection, relative humidity and global radiation - are measured atall urban background stations.

Apart from PM10 and TSP all parameters were recorded as ½-hour av-erages. PM10, TSP and elements in the particles were measured as 24hour averages. At the three stations in Copenhagen also ½-hour aver-ages of PM10 were recorded.

Short descriptions of the measured pollutants are given in the appen-dix. The actually applied measurement methods are listed at the Webaddress: LUFT.DMU.DK

Table 2-1 Stations in the LMP IV network and the Copenhagen network included in this report in 2002.

Name Street/location Type Remarks

Copenhagen/1257 Jagtvej Street

Copenhagen/1259 H.C. Ørsted Institute Urban background PM10 started April 2002

Copenhagen/1103 H.C. Andersens Boulevard Street Copenhagen Municipality

Århus/6153 Banegårdsgade Street

Århus/6159 Valdemarsgade Urban Background Measurements startedAug. 2001

Odense/9155 Albanigade Street

Odense/9159 Town hall in Odense Urban background

Aalborg/8151 Vesterbro Street

Aalborg/8159 Dept. for Envir. and Urban Af-fairs

Urban background

Lille Valby/2090 - Rural

Keldsnor/9055 - Rural

Averaging time

Other information

11

3 Nitrogen oxides

3.1 Yearly Statistics

Table 3-1 Nitrogen dioxide (NO2) 2002. All parameters are calculated with hourly averages.

Unit: µg/m3 Number Average Median 98. percentile 19. highest

Traffic:

Copenhagen/1257 8659 47 45 101 122

Copenhagen/1103 8598 61 59 119 142

Århus/6153 8659 44 41 100 125

Odense/9155 8575 37 29 103 133

Aalborg/8151 8453 33 29 85 111

Urban Background:

Copenhagen/1259 8037 20 16 58 75

Århus/6159 8712 26 22 72 96

Odense/9159 8701 18 15 50 68

Aalborg/8159 8624 17 14 54 94

Rural:

Lille Valby/2090 8349 12 9 38 50

Keldsnor/9055 8717 9 6 37 51

Limit values >7884 40 200

Table 3-2 Nitrogen oxide (NO) 2002. All parameters are calculated with hourly averages.

Unit: µg/m3 Number Average Median 98. percentile 19. highest

Traffic:

Copenhagen/1257 8659 45 32 160 344

Copenhagen/1103 8598 76 60 243 423

Århus/6153 8659 40 27 175 320

Odense/9155 8574 33 12 179 337

Aalborg/8151 8456 52 33 222 370

Urban Background:

Copenhagen/1259 8037 4 2 27 72

Århus/6159 8712 9 4 82 210

Odense/9159 8701 4 2 28 91

Aalborg/8159 8624 6 2 43 197

Rural:

Lille Valby/2090 8352 2 1 10 52

Keldsnor/9055 8717 1 0 7 21

12

The limit values are implemented through EU Council Directive (EC1999) and a national Regulation from the Ministry of Environment(Miljøministeriet 2003A).

13

3.2 Episodes

Table 3-3 Episodic results for Nitrogen dioxide (NO2) 2002. All parameters are calculated with hourly av-erages.

Unit: µg/m3 Max. 3 hours Date:hour Max. hour Date:hour

Traffic:

Copenhagen/1257 128 021021: 6 146 021021: 6

Århus/6153 149 020828:13 178 020828:15

Copenhagen/1103 123 020827: 5 149 021021: 6

Odense/9155 309 021217: 8 383 021217: 8

Aalborg/8151 106 020410:20 127 020411: 7

Urban Background:

Copenhagen/1259 78 020330:19 93 020330: 19

Århus/6159 93 020402: 5 157 021021: 7

Odense/9159 74 021101:15 84 020912: 7

Aalborg/8159 95 021212: 7 132 020410: 6

Rural:

Lille Valby/2090 54 020103: 8 61 020409: 8

Keldsnor/9055 54 020106: 5 71 020421:17

Alert threshold 400 - - -

Table 3-4 Episodic results for Nitrogen oxide (NO) 2002. All parameters are calculated with hourly aver-ages.

Unit: µg/m3 Max. 3 hours Date:hour Max. hour Date:hour

Traffic:

Copenhagen/1257 471 021021: 5 709 021021: 6

Copenhagen/1103 456 020103: 7 871 020919: 5

Århus/6153 394 021021: 5 715 021021: 7

Odense/9155 639 021217: 9 909 021217:10

Aalborg/8151 422 021212:12 486 021212: 8

Urban Background:

Copenhagen/1259 95 020107: 7 190 021127:17

Århus/6159 253 021218:19 669 021021: 7

Odense/9159 142 021015:21 205 020912: 7

Aalborg/8159 271 021212: 8 368 021212: 9

Rural:

Lille Valby/2090 86 020103: 9 192 020103:10

Keldsnor/9055 24 020110:18 47 020421:17

14

The Alert threshold is given in EU Council Directive (EC, 1999) andimplemented through a national Regulation from the Ministry of En-vironment (Miljøministeriet 2003A).

With reference to the definition of the alert threshold, the lowest one-hour values are calculated for all consecutive three-hour periods. Thehighest of these one-hour values are listed in the table in the column"Max. 3 hour". The alert threshold will, in practice, never be exceededin Denmark.

3.3 Trends

NO2 - annual averages

0

10

20

30

40

50

60

70

82 84 86 88 90 92 94 96 98 00 02

µg

/m3

Copenhagen/1257 Copenhagen/1103 Århus /6153 Odens e/9155 Aalborg/8151

0

20

40

60

80

100

120

140

82 84 86 88 90 92 94 96 98 00 02

NO - annual averages

µg

/m3

Figure 3-1 The graphs show the time series for the annual average valuesmeasured at street stations. Previous results from Copenhagen/1103 can befound at the Web-pages of the Copenhagen Environmental Protection Age-genncy (www. Miljoe.kk.dk).

15

NO2 - annual averages

0

5

10

15

20

25

30

82 84 86 88 90 92 94 96 98 00 02

µg

/m3

Copenhagen/1259 Århus/6159 Odense/9159Aalborg/8159 Lille Valby/2090 Keldsnor/9055

0

2

4

6

8

10

12

14

16

18

20

82 84 86 88 90 92 94 96 98 00 02

NO - annual averages

µg

/m3

Figure 3-2 The graphs show the time series for the annual average valuesmeasured at urban background and rural stations.

16

17

4 Ozone

4.1 Annual statistics

The target values and long time objectives are given in the EU Coun-cil Directive (EC, 2002) and implemented through a national Regula-tion from the Ministry of Environment (Miljøministeriet 2003B).

Number of information to the public due to exceedance of the infor-mation threshold (180 µg/m3) in 2002: 0.

Number of information to the public due to exceedance of the alertthreshold (240 µg/m3) in 2002: 0.

Table 4-1 Ozone (O3) 2002. All parameters are calculated with one-hour average values. The eight hourvalues are calculated as a moving average based on hourly measurements. For the "26. highest 8 hour"value is used the highest daily 8 hour values calculated as described in the EU Directive 2002/3/EC.

Unit: µg/m3 Number ofresults

Average Median Max. 8hours

26. highest8 hour

Max. 1hour

AOT40µg/m3.h

Urban Background:

Århus/6159 8729 50 53 125 97 141 4560

Odense/9159 7672 52 54 132 104 157 8970

Aalborg/8159 8160 51 54 120 93 131 2299

Rural

Lille Valby/2090 8347 54 56 144 104 155 5382

Keldsnor/9055 8734 63 66 150 116 161 9104

Traffic

Copenhagen/1257 8664 29 28 73 64 90 1

Copenhagen/1103 6781 29 25 105 72 143 374

Target value >7884 - - - 120 - 18 000

Long term objective >7884 - - 120 - - 6 000

18

4.2 Trends

O3 - annual averages

0

10

20

30

40

50

60

70

92 93 94 95 96 97 98 99 00 01 02

µg

/m3

Copenhagen/1259 Århus /6159 Odens e/9159 Aalborg/8159

Lille Valby/2090 Kelds nor/9055 Copenhagen/1257 Copenhagen/1103

Figure 4-1 Annual average values. Previous results from Copenhagen/1103 canbe found at the Web-pages of the Copenhagen Environmental Protection Age-genncy (www. Miljoe.kk.dk).

O3 - monthly averages

0

20

40

60

80

100

91 92 93 94 95 96 97 98 99 00 01 02

µg/m

3

Copenhagen/1259 Odense/9159 Aalborg/8159 Lille Valby/2090 Keldsnor/9055

Figure 4-2 Monthly average values for urban background and rural stations.

19

5 Carbon monoxide

5.1 Annual statistics

The limit value is implemented through EU Council Directive (EC,2000) and a national Regulation from the Ministry of Environment(Miljøministeriet 2003B).

The guideline values are proposed in WHO, 2000. (Air QualityGuidelines for Europe, Second Edition, WHO Regional Publications,European Series, No. 91, Copenhagen 2000).

Table 5-1 Annual statistics for carbon monoxide (CO) 2002. All parameters are calculated with hourly av-erage. The 8-hour values are calculated as a moving average based on hourly results.

Unit: µg/m3 Number Average Median 98-percentile 99.9-percentile Max. 8-hours Max hour

Traffic:

Copenhagen/1257 8669 1037 877 2781 6140 4605 9553

Copenhagen/1103 8670 922 813 2392 3982 2928 6210

Århus/6153 7918 606 525 1741 3575 2562 4715

Odense/9155 8702 750 548 2387 3885 3322 5504

Aalborg/8151 8718 862 705 2537 3921 3465 4684

Urban Background:

Copenhagen/1259 8045 328 284 786 1528 1174 2381

Limit value - - - - - 10 000 -

Guideline values - - - - - 10 000 30 000

20

5.2 Trends

CO - Annual average

0

500

1000

1500

2000

94 95 96 97 98 99 00 01 02

µg

/m3

Copenhagen/1257 Copenhagen/1103 Århus /6153

Odens e/9155 Aalborg/8151 Copenhagen/1259

CO - Annual 8 hour max.

0

2000

4000

6000

8000

10000

94 95 96 97 98 99 00 01 02

µg

/m3

Figure 5-1 Annual average values and highest 8-hour average. Previuos resultsfrom Copenhagen/1103 can be found at the Web-pages of the CopenhagenEnvironmental Protection Agegenncy (www. Miljoe.kk.dk).

21

6 Benzene and Toluene

6.1 Annual statistics

The limit value is implemented through EU Council Directive (EC,2000) and a national Regulation from the Ministry of Environment(Miljøministeriet 2003B).

Table 6-2 Annual statistics for Toluene 2002. The 7 days results are calcu-lated as a moving average based on daily averages.

Unit: µg/m3 Number ofresults

Average Max.

7 days

Max.

1 hour

Copenhagen/1257 6998 15.8 83 254

Guideline value - - 260 -

The guideline and lifetime risk level are established by WHO (WHO,2000).

Table 6-1 Annual statistics for Benzene 2002. All values are calculated as 1hour averages. The 8 hours results are calculated as a moving average. Thelife time risk level is defined as the concentration that through a lifelong ex-posure is estimated to give a excess risk of 1:105 for developing cancer.

Unit: µg/m3 Numberof results

Average Max.

8 hours

Max.

1 hour

Copenhagen/1257 6998 3.6 18 38

Limit value >7784 5 - -

Life time risk level at 1:105 1.7

22

23

7 Particles (TSP, PM10)

7.1 Annual statistics

The PM10 mass in the following are determined by weighing the ex-posed filters after conditioning for at least seven days at 52% RH and23 0C.

+) N.B. TSP (Total Suspended Particulate matter). At street stationsthe TSP concentration is around 1.4 times the PM10 concentration.The values cannot be compared to the limit values.

The limit values are implemented through EU Council Directive (EC,1999) and a national Regulation from the Ministry of Environment(Miljøministeriet 2003A).

At some stations there are too few measurements to a valid compari-son with the limit values. In these cases the 90-percentile will give abetter impression of the compliance with the limit value that must notbe exceeded more than 35 times every year.

7.2 Trends

Up till 2000 the particulate matter was measured as Total suspendedparticulate matter (TSP) corresponding to particles with a diameterup to around 25 µm. The exact cut-off depended however strongly onthe wind velocity. From 2001 PM10 measurement was started at allstations except Copenhagen/1103 where the TSP sampling was con-

Table 7-1 Annual statistics for PM10 2002. All parameters are calculated as daily averages. The limit valuesin parenthesis are indicative values valid from 2010. They will be reviewed before 2010.

Unit µg/m3 Number ofresults

Average 36.highestresult

90 percen-tile

95 percen-tile

8.highestresult

Max. day

Traffic

Copenhagen/1257 324 36 57 58 68 87 135

Copenh./1103 +) 357 77 122 123 142 159 202

Århus/6153 336 30 48 49 57 64 111

Odense/9155 349 33 54 55 64 74 127

Aalborg/8151 340 32 51 52 64 72 102

Urban background

Copehhagen/1259 223 25 36 44 51 52 83

Århus/6159 276 24 37 40 48 51 58

Aalborg/8159 298 25 40 42 54 64 88

Rural

Lille Valby/2090 311 27 45 48 60 67 106

Keldsnor/9055 326 30 48 48 58 70 178

Limit values >329 40(20) 50 - - (50) -

24

tinued. The TSP is around 30 % higher than PM10 at the street stations,and the difference is less at rural sites.

Annual averages

0

20

40

60

80

100

120

82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 00 01 02

µg

/m3

Copenhagen/1257 Copenhagen/1103 Å rhus/6153 Odense/9155 A alborg/8151

TSP PM10

Figure 7-1 Annual averages for TSP and PM10 measured at street stations. Re-sults from 200 and earlier are for TSP, while later results are for PM10 - exceptfor Copenhagen/1103, where TSP measurements are continued.

Annual averages

0

20

40

60

80

100

120

82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 00 01 02

µg

/m3

Copenhagen/1259 Å rhus/6159 A lborg/8159 Lille V alby /2090 Keldsnor/9055

TSP PM 10

Figure 7-2 Annual averages for TSP and PM10 measured at urban backgroundand rural stations.

25

8 Heavy Metals

8.1 Annual statistics

+) Measured in TSP (Total suspended particulate matter). Most of theheavy elements are present in particles. The heavy metals are pri-marily found in fine particles. The TSP and PM10 results are inmost cases comparable because the heavy metals primarily arefound in fine particles.

*) Some kind of threshold values will be implemented within a fewyears.

The limit value for Pb is found in EU Council Directive (EC, 1999). AnEU Council Directive including i.a. Ni, As and Cd is expected to beadapted in 2002 or 2003.

The guidelines and life time risk for the carcinogenic metals are es-tablished by WHO (WHO, 2000).

Table 8-1 Annual statistics for Vanadium (V), Chromium (Cr), Manganese (Mn), Nickel (Ni), Cupper (Cu),Zink (Zn), Arsenic (As), Selenium (Se), Cadmium (Cd) and Lead (Pb) measured in PM10 during 2002. Thelifetime risk level is defined as the concentration that through a lifelong exposure is estimated to give a ex-cess risk of 1:105 for developing cancer. The filters are occasionally contaminated with Cr, Ni, Cu and Zn.The out-layers for these elements are excluded before average calculation. At urban background and ru-ral stations the contamination with Cr still contributes with a comparable amount to the average values.

Unit: ng/m3 V Cr Mn Ni Cu Zn As Se Cd Pb

Traffic

Copenhagen/1257 7.17 7.96 13.9 4.2 60.3 46 0.7 0.5 <1.5 15.3

Copenhagen/1103 +) 10.0 16.7 77.6 4.6 96.1 113.0 0.6 0.4 < 0.8 25.5

Århus/6153 7.1 4.9 9.9 5.9 25.8 34.2 0.7 0.9 <1.5 8.5

Odense/9155 4.8 5.3 15.7 2.8 34.5 57.1 0.8 0.6 <1.5 11.9

Aalborg/8151 4.3 4.7 9.8 2.8 37.8 43.5 0.6 0.5 <1.5 9.3

Urban background

Copenhagen/1259 6.5 - 6.7 3.1 9.2 23.9 0.6 0.5 <1.5 7.1

Århus/6159 5.5 - 5.9 4.6 6.6 23.2 0.7 0.5 <1.5 5.6

Aalborg/8159 3.7 - 6.2 2.2 5.8 23.2 0.7 0.5 <1.5 5.5

Rural

Lille Valby/2090 4.5 - 5.5 2.1 4.2 23.9 0.9 0.5 <1.5 6.2

Keldsnor/9055 6.6 - 3.4 2.8 3.9 23.3 0.5 0.7 <1.5 6.9

Limit values *) *) *) 500

Guideline value 1000 150 5

Life time risk level at 1:105 25 6.6

26

8.2 Trends

Cr

0

5

10

15

20

25

83-84 87-88 91-92 95-96 99-00

M n

0

20

40

60

80

100

83-84 87-88 91-92 95-96 99-00

Zn

0

50

100

150

83-84 87-88 91-92 95-96 99-00

Copenhagen/1257 Aalborg/8151 Keldsnor/9055 Copenhagen/1103

V

0

10

20

30

83-84 87-88 91-92 95-96 99-00

Cu

0

20

40

60

80

100

83-84 87-88 91-92 95-96 99-00

Pb

1

10

100

1000

83-84 87-88 91-92 95-96 99-00

Figure 8-1 Biannual averages from selected stations for some Heavy Metals in particulate matter.Until 2000 in TSP and later in PM10 – except for Copenhagen/1103 where TSP measurements con-tinue. y-axis units are ng/m3. (Note that the scale for Pb is logarithmic.)

27

9 Sulphur Compounds

9.1 Annual statistics

The limit values are implemented through EU Council Directive (EC,1999) and a national Regulation from the Ministry of Environment(Miljøministeriet 2003A).

Table 9-1 Annual statistics for SO2 2002. All parameters are calculated based on hourly averages.

Unit: µg/m3 Numberof results

Averageyear

Averagewinter

Median 98-percentile

Max.Hour

4. highestday

TrafficCopenhagen/1103 8086 3.8 3.8 2.8 13 43 9Aalborg/8151 8689 3.8 3.9 2.9 13 29 9Limit values >7884 20 20 350 25

Table 9-2 Annual averages for particulate sulphur (S) measured in PM10

2002. Measurements are daily averages.

Unit: µg(S)/m3 Number of results AverageTrafficCopenhagen/1257 330 1.02Copenhagen/1103 359 1.22Århus/6153 336 1.00Odense/9155 351 1.05Aalborg/8151 354 0.90Urban backgroundCopenhagen/1259 234 0.91Århus/6159 292 0.95Aalborg/8159 315 0.84RuralLille Valby/2090 320 0.92Keldsnor/9055 328 1.10

28

9.2 Trends

SO2 - annual averages

0

5

10

15

20

25

30

82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 00 01

µg

/m3

Copenhagen/1257 Odense/9155 Aalborg/8151 Lille Valby/2090

Figure 9-1 Annual averages for SO2 and particulate sulphur

S (particulate) - annual averages

0

0.5

1

1.5

2

2.5

3

3.5

82 84 86 88 90 92 94 96 98 00 02

µg

/m3

Copenhagen/1257 Copenhagen/1103 Århus/6153 Odense/9155 Aalborg/8151

TSP PM10

Figure 9-2 Annual averages particulate sulphur for street stations. The par-ticulate sulphur from 2000 and earlier is determined in TSP, and the 2001 re-sults and later are for PM10 - except for Copenhagen/1103, where TSP meas-urements are continued.

29

S (particulate) - annual averages

0

0.5

1

1.5

2

2.5

3

82 84 86 88 90 92 94 96 98 00 02

µg

/m3

Copenhagen/1259 Århus/6159 Aalborg/8159 Lille Valby/2090 Keldsnor/9055

TSP PM10

Figure 2 Annual averages particulate sulphur for urban background and ru-ral stations. The particulate sulphur from 2000 and earlier is determined inTSP, and the 2001 results and later are for PM10

30

31

References

EC (1996): Directive 96/62/EC of September 27 on ambient air qual-ity assessment and management. J. Europ. Commun. L296/55.

EC (1999): Directive 1999/30/EC of 22 April 1999 relating to limitvalues for sulphur dioxide, nitrogen dioxide and oxides of nitrogen,particulate matter and lead in ambient air. J. Europ. Commun.L163/41.

EC (2000): Directive of the European Parliament and of the council2000/69/EC of 16 November 2000 on limit values for benzene andcarbon monoxide in ambient air. J. Europ. Commun. L313/12.

Directive 2002/3/EC of the European Parliament and of the Council of12 February 2002 relating to ozone in ambient air Official Journal L067 /14.

Miljøministeriet (2003A): Bekendtgørelse om grænseværdier forluftens indhold af visse forurenende stoffer. Bekendtgørelse nr. 58 af23. Januar 2003. (In Danish). Ministry of Environment; Copenhagen,Denmark.

Miljøministeriet (2003B): Bekendtgørelse om mål- og grænseværdierfor luftens indhold af visse forurenende stoffer. In preparation. (InDanish). Ministry of Environment; Copenhagen, Denmark.

WHO (2000): Air Quality Guidelines for Europe, Second Edition,WHO Regional Publications, European Series, No. 91, Copenhagen2000. See also (http://www.who.int/peh/air/Airqualitygd.htm)

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33

Danish summary - Dansk resumé

Rapporten præsenterer resultaterne fra overvågningsprogrammet forluftkvalitet i danske byer (LMP IV) for 2002. Formålet med pro-grammet er at fastlægge koncentrationer af skadelige stoffer i luften idanske byer, følge udviklingen af koncentrationerne og vurdere kil-derne til de enkelte stoffer. Målingerne bruges til at vurdere effektenaf allerede gennemførte tiltag og beregne virkningen af mulige frem-tidige tiltag. Desuden tjener resultaterne som videnbasis for en rækkevidenskabelige undersøgelser, fx vurdering af små partiklers effektpå sundheden.

Der er fastsat grænseværdier for flere af de målte stoffer. Grænse-værdierne skal overholdes fra 2005 eller 2010. Frem til da er det dogtilladt at overskride disse grænseværdier indenfor en fastsat margin,som løbende reduceres. En detaljeret beskrivelse af gældende mål- oggrænseværdier og deres gennemførelse findes i bekendtgørelser fraMiljøministeriet (se referencerne Miljøministeriet 2003A og 2003B) .Bekendtgørelserne er baseret på EU-direktiver (EC 1996, 1999, 2000og 2003).

De væsentligste konklusioner er at:

- indholdet af kvælstofdioxid (NO2) overskrider grænseværdierne påflere målestationer, og på en enkelt målestation er den tilladte marginoverskredet.

- indholdet af partikler mindre end 10 µm (PM10) overskrider grænse-værdierne mange steder. Den tilladte margin er ikke overskredet.

- der ikke er fastsat egentlige grænseværdier for ozon (O3) men kun"målværdier" og ”langsigtede målsætninger” (hensigtsværdier). Flerelangsigtede målsætninger er overskredet på flere stationer i 2002.

- De øvrige målte stoffer findes i koncentrationer under grænsevær-dierne, og for flere stoffer (fx svovldioxid og bly) er indholdet faldetkraftigt siden målingernes start.

Der er bred enighed blandt forskere og rådgivere i EU om, at grund-laget for fastsættelse af grænseværdier for partikler er meget mangel-fuldt. Blandt andet er kendskabet til indholdet af naturlige partikler(jord m.m.) i luften meget mangelfuldt. Der er allerede nu fastsat vej-ledende grænseværdier for partikler i luft gældende fra 2010. I er-kendelse af den mangelfulde viden er det imidlertid i EU direktivetom grænseværdier for PM10 bestemt, at de vejledende grænseværdierfor 2010 skal tages op til revision i løbet af de nærmeste år.

En stor del af forureningen med partikler og ozon skyldes forure-ningsudslip fra andre europæiske lande. Løsningen på mange af pro-blemerne må derfor findes på fælles europæisk plan.

34

35

Appendix

Pollutants measured in the LMP Network

NO and partly NO2 are formed by combustion at high temperatures.The main sources are power plants and traffic. At the street stationsthe traffic is the main source. The application of catalytic converter inthe exhaust reduces the emission considerably. NO is relativelyharmless, but NO2 can cause respiratory problems.

Most of the NO2 in the urban atmosphere is produced by oxidation ofnitrogen monoxide (NO) by ozone (O3). The reaction will take placeimmediate, if sufficient O3 is present. O3 is often the limiting compo-nent for a complete oxidation in the street canyons, but practically allNO is oxidised at the urban background and rural stations. Within afew hours the NO2 is further oxidised to nitrate and/or nitric acid,which may cause acid precipitation and eutrofication. NO2 is a toxicgas, which may cause respiratory problems. There are limit values forthe allowed concentration of NO2 in the atmosphere.

O3 is formed by photochemical reactions (i.e. by the influence of sun-light) between nitrogen oxides and volatile organic compounds(VOC’s). The VOC’s can be of natural and anthropogenic origin. Themajor part of the O3 measured in Denmark originates from sourcesoutside the country. Usually the highest concentrations are found atrural and urban background sites. O3 is removed by NO at streetlevel. O3 is a toxic gas, which may cause respiratory problems anddamage on crops and forests. There are so-called target values for theconcentration of O3 in the atmosphere.

The main source of CO in urban air is petrol-fuelled cars. The CO isformed due to incomplete combustion. The application of catalyticconverter in the exhaust reduces the emission considerably. CO isonly slowly removed from the atmosphere. CO is a toxic gas that mayprevent the uptake of oxygen in the blood. There are limit values forthe allowed concentration of CO in the atmosphere.

Benzene is present in petrol. It may also be formed in engines due toincomplete combustion. Since 1994 the benzene content i petrol hasbeen reduced by up to a factor of 5. The concentration in the atmos-phere is reduced correspondingly. Benzene is a carcinogenic gas.There is a limit value for the average content in the atmosphere.

Many different VOCs are present in the air. Several of these areemitted by incomplete combustion in e.g. engines and wood burningstoves. Several of the VOC’s are carcinogenic. Limit values will beimplemented for PAH (Polycyclic Aromatic Hydrocarbones). Of theVOC’s only benzene, toluene and xylenes are measured routinely inLMP IV at present.

The main sources for PM10 are resuspended dust and combustion.PM10 particles are also created in the atmosphere by oxidation of ni-

Nitrogen oxides (NO andNO2)

Nitrogen dioxide (NO2)

Ozone (O3)

Carbon monoxide (CO)

Benzene

Other volatile organiccompounds (VOC’s)

Particles smaller than 10µm(PM10)

36

trogen dioxide and sulphur dioxide. The submicron particles, whichare formed by combustion and chemical reactions in the atmosphere,are suspected to be the most harmful for the health. There are still alack of knowledge about the connection between health effects andparticle size. Limit values for the PM10 concentration in the atmos-phere are implemented at present. The limit values will most likelybe revised in a few years, when better knowledge about the adversehealth effects of fine particles influence on health has been obtained.

There are a number of different HM’s in the atmosphere. They areemitted from e.g. coal and oil fired power plants, waste incineratorsand industries. HM’s may also be emitted from traffic due to wear onengines, tires and brake pads. Several HM’s are toxic even in lowconcentrations and a few also carcinogenic. A limit value is imple-mented for lead. In 2002 or 2003 limit values are expected to be im-plemented for arsenic, cadmium, nickel and mercury. WHO has pro-posed guideline values for the toxic non-carcinogenic and estimatedlife time risks for the carcinogenic HM’s.

Sulphur dioxide (SO2) is formed by burning of fossil fuel and bio-mass. The SO2 is oxidised in the atmosphere to particulate sulphuricacid and sulphate. The conversion time depends strongly of the tem-perature and humidity in the air. It is typically of the order of oneday. Sulphuric acid contributes to “acid rain” and the deposition ofsulphate causes damage to sensitive ecosystems. During the last 20years the reduction of sulphur in fossil fuel and improved flue gascleaning has reduced the concentration of SO2 with one order ofmagnitude. SO2 may cause respiratory problems. There are limit val-ues for the allowed concentration of SO2 in the atmosphere.

Heavy metals (HM’s)

Sulphur compounds

37

National Environmental Research Institute

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450A

ir Quality M

onitoring Programm

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National Environmental Research Institute ISBN 87-7772-713-4Ministry of the Environment ISSN 1600-0048

The air quality in Danish cities has been monitored continuously since1982 within the Danish Air Quality (LMP) network. The aim has beento follow the concentration levels of toxic pollutants in the urbanatmosphere and to provide the necessary knowledge to assess thetrends, to perform source apportionment, and to evaluate the chemicalreactions and the dispersion of the pollutants in the atmosphere. In2002 the air quality was measured in four Danish cities and at twobackground sites. NO2 and PM10 were at several stations found inconcentrations above the new EU limit values, which the MemberStates have to comply with in 2005 and 2010. While the concentrationsfor most other pollutants have been strongly decreasing since 1982, onlya slight decrease has been observed for NO2.